Fungicides

ABSTRACT

Fungicidal compounds having the formula (I): ##STR1## in which any two of K, L and M are nitrogen and the other is CY wherein Y is H, halogen, C 1-4  alkyl, C 1-4  alkoxy, cyano, nitro or trifluoromethyl; n is 0 or 1 and X is an optionally substituted aromatic or heteroaromatic ring.

This is a division of application Ser. No. 07/544,544, filed Jun. 28,1990, now U.S. Pat. No. 5,124,329.

This invention on relates to derivatives of propenoic acid useful asfungicides, to processes for preparing them, to fungicidal compositionscontaining them, and to methods of using them to combat fungi,especially fungal infections of plants.

There is described in EP-A-0260794 a range of fungicidal compounds whichare methyl 2-(optionally substituted)heterocyclyloxy(orthio)phenyl-3-methoxypropenoates. The heterocyclic ring is six-membered,C-linked and contains 2 to 4 nitrogen atoms. Included are triazinyloxycompounds.

According to the present invention there are provided compounds havingthe formula (I): ##STR2## in which any two of K, L and M are nitrogenand the other is CY wherein Y is H, halogen, C₁₋₄ alkyl (for example,methyl), C₁₋₄ alkoxy (for example, methoxy), cyano, nitro ortrifluoromethyl; n is 0 or 1; and X is an optionally substitutedaromatic or heteroaromatic ring.

Because of the unsymmetrically substituted double bond of the propenoategroup, the compounds of the invention may be obtained in the form ofmixtures of (E) and (Z) geometric isomers. However, these mixtures canbe separated into individual isomers, and this invention embraces suchisomers and mixtures thereof in all proportions including those whichconsist substantially of the (Z)-isomer and those which consistsubstantially of the (E)-isomer. The (E)-isomer, in which the groups--CO₂ CH₃ and --OCH₃ are on opposite sides of the olefinic bond of thepropenoate group, are the more fungicidally active and form a preferredembodiment of the invention.

The ring ##STR3## in formula (I) is a triazine ring. It may be asymmetrical triazine ring in which K and M are both nitrogen and L is CYor an unsymmetrical triazine ring in which either K and L are bothnitrogen and M is CY or L and M are both nitrogen and K is CY.

The group Y is typically H or halogen, suitably chlorine.

The group X may be any optionally substituted aromatic or heteroaromaticring. When it is an optionally substituted aromatic ring the aromaticring is suitably phenyl. When it is an optionally substitutedheteroaromatic ring the heteroaromatic ring may be, for example, one ofthe following rings, in each case linked from any atom of the ring Xwhich valency allows: furan, thiophene, pyrrole, imidazole, pyrazole,thiazole, isothiazole, oxazole, isoxazole, 1,2,4-triazole,1,2,3-triazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole, pyridine,pyrimidine, pyrazine, pyridazine, 1,2,4-triazine or 1,3,5-triazine.

Optional substituents of the aromatic or heteroaromatic ring X includeone or more of halogen, C₁₋₄ alkyl, C₃₋₆ cycloalkyl, C₂₋₄ alkenyl, C₂₋₄alkynyl, C₂₋₄ alkenyloxy, C₂₋₄ alkynyloxy, phenyl, benzyloxy, cyano,isocyano, thiocyonato isothiocyanato, nitro, NR¹ OR², N₃, NHCOR¹, NR¹COR², NCHNR¹ R², NH═CHNR¹ R², NHSO₂ R¹, OR¹, OCOR¹, OSO₂ R¹, SR¹, SOR¹,SO₂ R¹, SO₂ OR¹, SO₂ NR¹ R², COR¹, CR¹ ═NOR², CHR¹ CO₂ R², CO₂ R¹, CONR¹R², CSNR¹ R², CH₃ O₂ C.C:CH.OCH₃, 1-(imidazol-1-yl)vinyl, a 5-memberedheterocyclic ring containing one, two or three nitrogen heteroatoms, ora 5- or 6-membered heterocyclic ring containing one or two oxygen orsulphur heteroatoms, optionally a nitrogen heteroatom and optionally oneor two oxo or thioxo substituents; or two substituents when ortho to oneanother, join to form a 5- or 6-membered aliphatic or aromatic ringoptionally containing one or more oxygen, sulphur or nitrogen atoms. R¹and R² are independently hydrogen, C₁₋₄ alkyl, C₂₋₄ alkenyl or phenyl.The aliphatic moieties of any of the substituents may themselves besubstituted with one or more of halogen, cyano, OR¹, SR¹, NR¹ R², SiR¹ ₃or OCOR¹ and the phenyl moieties of any of the substituents maythemselves be substituted with one or more of halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, nitro or cyano.

Typical optional substituents of the aromatic or heteroaromatic ring Xare halogen, C₁₋₄ alkyl, C₃₋₆ cycloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl,C₂₋₄ alkenyloxy, C₂₋₄ alkynyloxy, phenyl, benzyloxy, cyano, isocyano,thiocyanato, isothiocyanato, nitro, NR¹ R², NHCOR¹, NHCONR¹ R², NHSO₂R¹, OR¹, OCOR¹, OSO₂ R¹, SR¹, SOR¹, SO₂ R¹, COR¹, CR¹ ═NOR², CO₂ R¹,CONR¹ R², When substituents are ortho to one another, they may join toform a 5- or 6-membered aliphatic or aromatic ring optionally containingone or more oxygen, sulphur or nitrogen atoms. R¹ and R² areindependently hydrogen, C₁₋₄ alkyl or phenyl. The aliphatic moieties ofany of the substituents may themselves be substituted with one or moreof halogen, cyano, OR¹ or OCOR¹ and the phenyl moieties of any of thesubstituents may themselves be substituted with one or more of halogen,C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro or cyano.

Alkyl groups contain from 1 to 4 carbon atoms and may be in the form ofstraight or branched chains. Examples are methyl, ethyl, iso-propyl,n-butyl and t-butyl. Cycloalkyl groups contain from 3 to 6 carbon atomsand include cyclopropyl and cyclohexyl.

Alkenyl and alkynyl groups contain from 2 to 4 carbon atoms and may bein the form of straight or branched chains. Examples are ethenyl, allyl,methylallyl and propargyl.

Halogen is typically fluorine, chlorine or bromine.

Aliphatic moieties which may be substituted include, in particular, C₁₋₄alkyl groups.

Of particular interest are compounds of formula (I) in which X isunsubstituted phenyl or phenyl substituted by halogen (especiallychlorine), C₁₋₄ alkyl, C₁₋₄ alkoxy, trifluoromethyl, cyano or nitro.

In one aspect the invention provides a compound of formula (I.1):##STR4## in which Y is H or chlorine and Q is H, halogen (especiallychlorine), cyano, nitro or trifluoromethyl.

In another aspect the invention provides a compound of formula (I.2):##STR5## in which Y is H or chlorine and Q is halogen, C₁₋₄ alkyl, C₁₋₄alkoxy (especially methoxy), cyano, nitro, trifluoromethyl or CH₃ O₂C.C:CH.OCH₃.

The invention is illustrated by the compounds listed in Tables I to VIwhich follow. Throughout these Tables the methyl 3-methoxypropenoategroup has the (E)-configuration

                                      TABLE I                                     __________________________________________________________________________     ##STR6##                                                                     Compound                     Melting                                          No.   X                    n Point (°C.)                                                                  Olefinic*                                  __________________________________________________________________________     1    C.sub.6 H.sub.5      0 152-4 7.43                                        2    2-FC.sub.6 H.sub.4   0 106-108                                                                             7.44                                        3    3-FC.sub.6 H.sub.4   0                                                   4    4-FC.sub.6 H.sub.4   0                                                   5    2-ClC.sub.6 H.sub.4  0                                                   6    3-ClC.sub.6 H.sub.4  0                                                   7    4-ClC.sub.6 H.sub.4  0 140-2 7.43                                        8    2-BrC.sub.6 H.sub.4  0                                                   9    2-cyano-C.sub.6 H.sub.4                                                                            0                                                   10   3-cyano-C.sub.6 H.sub.4                                                                            0                                                   11   4-cyano-C.sub.6 H.sub.4                                                                            0 65-70 7.42                                        12   2-isocyano-C.sub.6 H.sub.4                                                                         0                                                   13   2-NO.sub.2C.sub.6 H.sub. 4                                                                         0 Gum   7.48                                        14   3-NO.sub.2C.sub.6 H.sub.4                                                                          0 160-2 7.44                                        15   4-NO.sub.2C.sub.6 H.sub.4                                                                          0 Foam  7.42                                        16   2-NH.sub.2C.sub.6 H.sub.4                                                                          0                                                   17   3-NH(CH.sub.3)C.sub.6 H.sub.4                                                                      0                                                   18   2-N(CH.sub.3).sub.2C.sub.6 H.sub.4                                                                 0                                                   19   2-NH.CHOC.sub.6 H.sub.4                                                                            0                                                   20   2-CH.sub.3 CO.NHC.sub.6 H.sub.4                                                                    0                                                   21   3-C.sub.6 H.sub.5 CO.NHC.sub.6 H.sub.4                                                             0                                                   22   2-H.sub.2 N.CONHC.sub.6 H.sub.4                                                                    0                                                   23   3-(C.sub.2 H.sub.5)NH.CONHC.sub.6 H.sub.4                                                          0                                                   24   2-CH.sub.3 SO.sub.2 NHC.sub.6 H.sub.4                                                              0                                                   25   3-C.sub.6 H.sub.5 SO.sub.2 NHC.sub.6 H.sub.4                                                       0                                                   26   2-HOC.sub.6 H.sub.4  0                                                   27   3-HOC.sub.6 H.sub.4  0                                                   28   4-HOC.sub.6 H.sub.4  0                                                   29   2-CH.sub.3 OC.sub.6 H.sub.4                                                                        0                                                   30   3-CH.sub.3 OC.sub.6 H.sub.4                                                                        0                                                   31   4-CH.sub.3 OC.sub.6 H.sub.4                                                                        0                                                   32   2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                                 0                                                   33   3-(2-FC.sub.6 H.sub.4 O)C.sub.6 H.sub.4                                                            0                                                   34   2-CH.sub.3 CO.sub.2C.sub.6 H.sub.4                                                                 0                                                   35   2-CH.sub.3 SO.sub.2 OC.sub.6 H.sub.4                                                               0                                                   36   3-(4-CH.sub.3C.sub.6 H.sub.4 SO.sub.2 O)C.sub.6 H.sub.4                                            0                                                   37   2-thiocyanato-C.sub.6 H.sub.4                                                                      0                                                   38   3-thiocyanato-C.sub.6 H.sub.4                                                                      0                                                   39   4-thiocyanato-C.sub.6 H.sub.4                                                                      0                                                   40   2-CH.sub.3 SC.sub.6 H.sub.4                                                                        0                                                   41   3-CH.sub.3 SC.sub.6 H.sub.4                                                                        0                                                   42   4-CH.sub.3 SC.sub.6 H.sub.4                                                                        0                                                   43   2-CH.sub.3 SOC.sub.6 H.sub.4                                                                       0                                                   44   2-CH.sub.3 SO.sub.2C.sub.6 H.sub.4                                                                 0                                                   45   4-CH.sub.3 (CH.sub.2).sub.3 SO.sub.2C.sub.6 H.sub.4                                                0                                                   46   2-CHOC.sub.6 H.sub.4 0                                                   47   3-CHOC.sub.6 H.sub.4 0                                                   48   4-CHOC.sub.6 H.sub.4 0                                                   49   2-CH.sub.3 COC.sub.6 H.sub.4                                                                       0                                                   50   3-C.sub.6 H.sub.5 COC.sub.6 H.sub.4                                                                0                                                   51   2-( .sub.--E)HON:CHC.sub.6 H.sub.4                                                                 0                                                   52   3-( .sub.--E)HON:CHC.sub.6 H.sub.4                                                                 0                                                   53   4-( .sub.--E)HON:CHC.sub.6 H.sub.4                                                                 0                                                   54   2-( .sub.--E)CH.sub.3 ON:CHC.sub.6 H.sub.4                                                         0                                                   55   2-( .sub.--E)HON:C(CH.sub.3)C.sub.6 H.sub.4                                                        0                                                   56   2-H.sub.2 NCOC.sub.6 H.sub.4                                                                       0                                                   57   3-H(CH.sub.3)NCOC.sub.6 H.sub.4                                                                    0                                                   58   4-(CH.sub.3).sub.2 NCOC.sub.6 H.sub.4                                                              0                                                   59   2-H.sub.2 NCSC.sub.6 H.sub.4                                                                       0                                                   60   2-H(CH.sub.3)NCSC.sub.6 H.sub.4                                                                    0                                                   61   2-CH.sub.3C.sub.6 H.sub.4                                                                          0                                                   62   3-CH.sub.3C.sub.6 H.sub.4                                                                          0                                                   63   4-CH.sub.3C.sub.6 H.sub.4                                                                          0                                                   64   2-C.sub.2 H.sub.5C.sub.6 H.sub. 4                                                                  0                                                   65   2-FCH.sub.2C.sub.6 H.sub.4                                                                         0                                                   66   2-BrCH.sub.2C.sub.6 H.sub.4                                                                        0                                                   67   2-ClCH.sub.2C.sub.6 H.sub.4                                                                        0                                                   68   2-cyanomethyl-C.sub.6 H.sub.4                                                                      0                                                   69   2-HOCH.sub.2C.sub.6 H.sub.4                                                                        0                                                   70   2-CH.sub.3 OCH.sub.2C.sub.6 H.sub.4                                                                0                                                   71   2-CH.sub.3 CO.sub.2 CH.sub.2C.sub.6 H.sub.4                                                        0                                                   72   3-cyanomethyl-C.sub.6 H.sub.4                                                                      0                                                   73   4-HOCH.sub.2C.sub.6 H.sub.4                                                                        0                                                   74   3-CH.sub.3 OCH.sub.2C.sub.6 H.sub.4                                                                0                                                   75   2-CH.sub.2 :CHC.sub.6 H.sub.4                                                                      0                                                   76   2-CH.sub.2 :CHCH.sub.2C.sub.6 H.sub.4                                                              0                                                   77   2-HC CC.sub.6 H.sub.4                                                                              0                                                   78   2-HC CCH.sub.2C.sub.6 H.sub.4                                                                      0                                                   79   3-CH.sub.2 :C(CH.sub.3)CH.sub.2C.sub.6 H.sub.4                                                     0                                                   80   2-CH.sub.2 :CHCH.sub.2 OC.sub.6 H.sub.4                                                            0                                                   81   2-HC  CCH.sub.2 OC.sub.6 H.sub.4                                                                   0                                                   82   2-C.sub.6 H.sub.5C.sub.6 H.sub.4                                                                   0                                                   83   3-C.sub.6 H.sub.5C.sub.6 H.sub.4                                                                   0                                                   84   4-C.sub.6 H.sub.5C.sub.6 H.sub.4                                                                   0                                                   85   2-C.sub.6 H.sub.5 OC.sub.6 H.sub.4                                                                 0                                                   86   3-C.sub.6 H.sub.5 OC.sub.6 H.sub.4                                                                 0                                                   87   4-C.sub.6 H.sub.5 OC.sub.6 H.sub.4                                                                 0                                                   88   2-(4-ClC.sub.6 H.sub.4 O)C.sub.6 H.sub.4                                                           0                                                   89   2-C.sub.6 H.sub.5 CH.sub.2 OC.sub.6 H.sub.4                                                        0                                                   90   2-cyano-4-ClC.sub.6 H.sub.3                                                                        0                                                   91   2-NO.sub.2 -4-FC.sub.6 H.sub.3                                                                     0                                                   92   2,4-di-ClC.sub.6 H.sub.3                                                                           0                                                   93   2,3-di-CH.sub.3 OC.sub.6 H.sub.3                                                                   0                                                   94   2-cyano-5-ClC.sub.6 H.sub.3                                                                        0                                                   95   2,6-di-cyano-C.sub.6 H.sub.3                                                                       0                                                   96   2-F-5-ClC.sub.6 H.sub.3                                                                            0                                                   97   3,5-di-CH.sub.3 OC.sub.6 H.sub.3                                                                   0                                                   98   3-cyano-4-FC.sub.6 H.sub.3                                                                         0                                                   99   2-NO.sub.2 -3-CH.sub.3 OC.sub.6 H.sub.3                                                            0                                                  100   3-CH.sub.3 O-5-cyano-C.sub.6 H.sub.3                                                               0                                                  101                                                                                  ##STR7##            0                                                  102                                                                                  ##STR8##            0                                                  103                                                                                  ##STR9##            0                                                  104   2,3-methylenedioxy-C.sub.6 H.sub.3                                                                 0                                                  105                                                                                  ##STR10##           0                                                  106                                                                                  ##STR11##           0                                                  107   Pyridin-2-yl         0                                                  108   Pyridin-3-yl         0                                                  109   Pyridin-4-yl         0                                                  110   Pyrimidin-2-yl       0                                                  111   Pyrimidin-4-yl       0                                                  112   Pyrimidin-5-yl       0                                                  113   Thien-2-yl           0                                                  114   Thien-3-yl           0                                                  115   C.sub.6 H.sub.5      1 78-80 7.41                                       116   2-FC.sub.6 H.sub.4   1                                                  117   3-FC.sub.6 H.sub.4   1                                                  118   4-FC.sub.6 H.sub.4   1                                                  119   2-ClC.sub.6 H.sub.4  1                                                  120   3-ClC.sub.6 H.sub.4  1                                                  121   4-ClC.sub.6 H.sub.4  1                                                  122   2-BrC.sub. 6 H.sub.4 1                                                  123   2-cyano-C.sub.6 H.sub.4                                                                            1                                                  124   3-cyano-C.sub.6 H.sub.4                                                                            1                                                  125   4-cyano-C.sub.6 H.sub.4                                                                            1                                                  126   2-isocyano-C.sub.6 H.sub.4                                                                         1                                                  127   2-NO.sub.2C.sub.6 H.sub.4                                                                          1                                                  128   3-NO.sub.2C.sub.6 H.sub.4                                                                          1                                                  129   4-NO.sub.2C.sub.6 H.sub.4                                                                          1                                                  130   2-NH.sub.2C.sub.6 H.sub.4                                                                          1                                                  131   3-NH(CH.sub.3)C.sub.6 H.sub.4                                                                      1                                                  132   2-N(CH.sub.3).sub.2C.sub.6 H.sub.4                                                                 1                                                  133   2-NH.CHOC.sub.6 H.sub.4                                                                            1                                                  134   2-CH.sub.3 CO.NHC.sub.6 H.sub.4                                                                    1                                                  135   3-C.sub.6 H.sub.5 CO.NHC.sub.6 H.sub.4                                                             1                                                  136   2-H.sub.2 N.CONHC.sub.6 H.sub.4                                                                    1                                                  137   3-(C.sub.2 H.sub.5)NH.CONHC.sub.6 H.sub.4                                                          1                                                  138   2-CH.sub.3 SO.sub.2 NHC.sub.6 H.sub.4                                                              1                                                  139   3-C.sub.6 H.sub.5 SO.sub.2 NHC.sub.6 H.sub.4                                                       1                                                  140   2-HOC.sub.6 H.sub.4  1                                                  141   3-HOC.sub.6 H.sub.4  1                                                  142   4-HOC.sub.6 H.sub.4  1                                                  143   2-CH.sub.3 OC.sub.6 H.sub.4                                                                        1                                                  144   3-CH.sub.3 OC.sub.6 H.sub.4                                                                        1                                                  145   4-CH.sub.3 OC.sub.6 H.sub.4                                                                        1                                                  146   2-C.sub.2 H.sub.5 OC.sub.6 H.sub.4                                                                 1                                                  147   3-(2-FC.sub.6 H.sub.4 O)C.sub.6 H.sub.4                                                            1                                                  148   2-CH.sub.3 CO.sub.2C.sub.6 H.sub.4                                                                 1                                                  149   2-CH.sub.3 SO.sub.2 OC.sub.6 H.sub.4                                                               1                                                  150   3-(4-CH.sub.3C.sub.6 H.sub.4 SO.sub.2 O)C.sub.6 H.sub.4                                            1                                                  151   2-thiocyanato-C.sub.6 H.sub.4                                                                      1                                                  152   3-thiocyanato-C.sub.6 H.sub.4                                                                      1                                                  153   4-thiocyanato-C.sub.6 H.sub.4                                                                      1                                                  154   2-CH.sub.3 SC.sub.6 H.sub.4                                                                        1                                                  155   3-CH.sub.3 SC.sub.6 H.sub.4                                                                        1                                                  156   4-CH.sub.3 SC.sub.6 H.sub.4                                                                        1                                                  157   2-CH.sub.3 SOC.sub.6 H.sub.4                                                                       1                                                  158   2-CH.sub.3 SO.sub.2C.sub.6 H.sub.4                                                                 1                                                  159   4-CH.sub.3 (CH.sub.2).sub.3 SO.sub.2C.sub.6 H.sub.4                                                1                                                  160   2-CHOC.sub.6 H.sub.4 1                                                  161   3-CHOC.sub.6 H.sub.4 1                                                  162   4-CHOC.sub.6 H.sub.4 1                                                  163   2-CH.sub.3 COC.sub.6 H.sub.4                                                                       1                                                  164   3-C.sub.6 H.sub.5 COC.sub.6 H.sub.4                                                                1                                                  165   2-( .sub.--E)HON:CHC.sub.6 H.sub.4                                                                 1                                                  166   3-( .sub.--E)HON:CHC.sub.6 H.sub.4                                                                 1                                                  167   4-( .sub.--E)HON:CHC.sub.6 H.sub.4                                                                 1                                                  168   2-( .sub.--E)CH.sub.3 ON:CHC.sub.6 H.sub.4                                                         1                                                  169   2-( .sub.--E)HON:C(CH.sub.3)C.sub.6 H.sub.4                                                        1                                                  170   2-H.sub.2 NCOC.sub.6 H.sub.4                                                                       1                                                  171   3-H(CH.sub.3)NCOC.sub.6 H.sub.4                                                                    1                                                  172   4-(CH.sub.3).sub.2 NCOC.sub.6 H.sub.4                                                              1                                                  173   2-H.sub.2 NCSC.sub.6 H.sub.4                                                                       1                                                  174   2-H(CH.sub.3)NCSC.sub.6 H.sub.4                                                                    1                                                  175   2-CH.sub.3C.sub.6 H.sub.4                                                                          1                                                  176   3-CH.sub.3C.sub.6 H.sub.4                                                                          1                                                  177   4-CH.sub.3C.sub.6 H.sub.4                                                                          1                                                  178   2-C.sub.2 H.sub.5C.sub.6 H.sub.4                                                                   1                                                  179   2-FCH.sub.2C.sub.6 H.sub.4                                                                         1                                                  180   2-BrCH.sub.2C.sub.6 H.sub.4                                                                        1                                                  181   2-ClCH.sub.2C.sub.6 H.sub.4                                                                        1                                                  182   2-cyanomethyl-C.sub.6 H.sub.4                                                                      1                                                  183   2-HOCH.sub.2C.sub.6 H.sub.4                                                                        1                                                  184   2-CH.sub.3 OCH.sub.2C.sub.6 H.sub.4                                                                1                                                  185   2-CH.sub.3 CO.sub.2 CH.sub.2C.sub.6 H.sub.4                                                        1                                                  186   3-cyanomethyl-C.sub.6 H.sub.4                                                                      1                                                  187   4-HOCH.sub.2C.sub.6 H.sub.4                                                                        1                                                  188   3-CH.sub.3 OCH.sub.2C.sub.6 H.sub.4                                                                1                                                  189   2-CH.sub.2 :CHC.sub.6 H.sub.4                                                                      1                                                  190   2-CH.sub.2 :CHCH.sub.2C.sub.6 H.sub.4                                                              1                                                  191   2-HC CC.sub.6 H.sub.4                                                                              1                                                  192   2-HC CCH.sub.2C.sub.6 H.sub.4                                                                      1                                                  193   3-CH.sub.2 :C(CH.sub.3)CH.sub.2C.sub.6 H.sub.4                                                     1                                                  194   2-CH.sub.2 :CHCH.sub.2 OC.sub.6 H.sub.4                                                            1                                                  195   2-HC CCH.sub.2 OC.sub.6 H.sub.4                                                                    1                                                  196   2-C.sub.6 H.sub.5C.sub.6 H.sub.4                                                                   1                                                  197   3-C.sub.6 H.sub.5C.sub.6 H.sub.4                                                                   1                                                  198   4-C.sub.6 H.sub.5C.sub.6 H.sub.4                                                                   1                                                  199   2-C.sub.6 H.sub.5 OC.sub.6 H.sub.4                                                                 1                                                  200   3-C.sub.6 H.sub.5 OC.sub.6 H.sub.4                                                                 1                                                  201   4-C.sub.6 H.sub.5 OC.sub.6 H.sub.4                                                                 1                                                  202   2-(4-ClC.sub.6 H.sub.4 O)C.sub.6 H.sub.4                                                           1                                                  203   2-C.sub.6 H.sub.5 CH.sub.2 OC.sub.6 H.sub.4                                                        1                                                  204   2-cyano-4-ClC.sub.6 H.sub.3                                                                        1                                                  205   2-NO.sub.2 -4-FC.sub.6 H.sub.3                                                                     1                                                  206   2,4-di-ClC.sub.6 H.sub.3                                                                           1                                                  207   2,3-di-CH.sub.3 OC.sub.6 H.sub.3                                                                   1                                                  208   2-cyano-5-ClC.sub.6 H.sub.3                                                                        1                                                  209   2,6-di-cyano-C.sub.6 H.sub.3                                                                       1                                                  210   2-F-5-ClC.sub.6 H.sub.3                                                                            1                                                  211   3,5-di-CH.sub.3 OC.sub.6 H.sub.3                                                                   1                                                  212   3-cyano-4-FC.sub.6 H.sub.3                                                                         1                                                  213   2-NO.sub.2 -3-CH.sub.3 OC.sub.6 H.sub.3                                                            1                                                  214   3-CH.sub.3 O-5-cyano-C.sub.6 H.sub.3                                                               1                                                  215                                                                                  ##STR12##           1                                                  216                                                                                  ##STR13##           1                                                  217                                                                                  ##STR14##           1                                                  218   2,3-methylenedioxy-C.sub.6 H.sub.3                                                                 1                                                  219                                                                                  ##STR15##           1                                                  220                                                                                  ##STR16##           1                                                  221   Pyridin-2-yl         1                                                  222   Pyridin-3-yl         1                                                  223   Pyridin-4-yl         1                                                  224   Pyrimidin-2-yl       1                                                  225   Pyrimidin-4-yl       1                                                  226   Pyrimidin-5-yl       1                                                  227   Thien-2-yl           1                                                  228   Thien-3-yl           1                                                  229   2,6-di-FC.sub.6 H.sub.3                                                                            1                                                  230   2- -n-C.sub.3 H.sub.7C.sub.6 H.sub.4                                                               1                                                  231   2-CF.sub.3C.sub.6 H.sub.4                                                                          1                                                  232   2- .sub.-i-C.sub.3 H.sub.7C.sub.6 H.sub.4                                                          1                                                  233   2- -n-C.sub.3 H.sub.7 OC.sub.6 H.sub.4                                                             1                                                  234   2- .sub.-i-C.sub.3 H.sub.7 OC.sub.6 H.sub.4                                                        1                                                  235   2- -n-C.sub.4 H.sub.9 OC.sub.6 H.sub.4                                                             1                                                  236   2-IC.sub.6 H.sub.4   1                                                  237   2- -n-C.sub.5 H.sub.11C.sub.6 H.sub.4                                                              1                                                  238   2- .sub.-i-C.sub.4 H.sub.9 OC.sub.6 H.sub.4                                                        1                                                  239   2- .sub.-s-C.sub.4 H.sub.9 OC.sub.6 H.sub.4                                                        1                                                  240   2- .sub.-t-C.sub.4 H.sub.9 OC.sub.6 H.sub.4                                                        1                                                  241   2- -n-C.sub.4 H.sub.9C.sub.6 H.sub.4                                                               1                                                  242   2-[( .sub.--E)CH.sub.3 O.sub.2 C.CCH.OCH.sub.3 ]C.sub.6 H.sub.4                                    1 Gum   7.43,7.49                                  243   3-CF.sub.3C.sub.6 H.sub.4                                                                          0 127-7 7.43                                       244   2-CH.sub.3 O-4-CH.sub.3C.sub.6 H.sub.3                                                             1                                                  245   2,4-di-CH.sub.3C.sub.6 H.sub.3                                                                     1                                                  246   2,4,6-tri-CH.sub.3C.sub.6 H.sub.2                                                                  1                                                  247   2,6-di-CH.sub.3C.sub.6 H.sub.3                                                                     1                                                  248   2-F-6-CH.sub.3 OC.sub.6 H.sub.3                                                                    1                                                  249   2-CH.sub.3 -4-ClC.sub.6 H.sub.3                                                                    1                                                  250   C.sub.6 F.sub.5      1                                                  251   3,4-methylenedioxy-C.sub.6 H.sub.3                                                                 1                                                  252   3,4-di-ClC.sub.6 H.sub.3                                                                           1                                                  253   2-CH.sub.3 O-4-FC.sub.6 H.sub.3                                                                    1                                                  254   3,4-di-CH.sub.3C.sub. 6 H.sub.3                                                                    1                                                  255   2,3,5-tri-CH.sub.3C.sub.6 H.sub.2                                                                  1                                                  256   2,4-di-FC.sub.6 H.sub.3                                                                            1                                                  257   2,4-di-ClC.sub.6 H.sub.3                                                                           1                                                  258   3,4,5-tri-CH.sub.3C.sub.6 H.sub.2                                                                  1                                                  259   3-cyanopyridin-2-yl  0                                                  260   5-CF.sub.3 -pyridin-2-yl                                                                           0                                                  261   2-CH.sub.3 -pyridin-3-yl                                                                           0                                                  262   2-Cl-pyridin-3-yl    0                                                  263   2-CH.sub.3 O-pyridin-4-yl                                                                          0                                                  264   5-Br-pryimidin-2-yl  0                                                  265   5-F-pyrimidin-2-yl   0                                                  266   4-Cl-pyrimidin-2-yl  0                                                  267   2-phenylpyrimidin-5-yl                                                                             0                                                  268   6-Cl-pyrazin-2-yl    0                                                  269   6-Cl-pyridazin-3-yl  0                                                  270   3-cyanopyridin-2-yl  1                                                  271   5-CF.sub.3 -pyridin-2-yl                                                                           1                                                  272   2-CH.sub.3 -pyridin-3-yl                                                                           1                                                  273   2-Cl-pyridin-3-yl    1                                                  274   2-CH.sub.3 O-pyridin-4-yl                                                                          1                                                  275   5-Br-pyrimidin-2-yl  1                                                  276   5-F-pyrimidin-2-yl   1                                                  277   4-Cl-pyrimidin-2-yl  1                                                  278   2-phenylpyrimidin-5-yl                                                                             1                                                  279   6-Cl-pyrazin-2-yl    1                                                  280   6-Cl-pyridazin-3-yl  1                                                  __________________________________________________________________________     *Chemical shift of singlet from olefinic proton on                            β-methoxypropenoate group (ppm from tetramethylsilane). Solvent:         CDCl.sub.3 unless otherwise stated.                                      

                  TABLE II                                                        ______________________________________                                         ##STR17##                                                                    ______________________________________                                    

Table II comprises 280 compounds of the general structure above with allthe values of X and n listed in Table I. That is, compounds numbers 1 to280 of Table II are the same as those of Table I except that the 3- and5-substituents of the 1,2,4-triazine ring in Table I are reversed inTable II.

                  TABLE II                                                        ______________________________________                                        Compound                     Melting                                          No.      X            n      Point (°C.)                                                                    Olefinic*                                ______________________________________                                        115      C.sub.6 H.sub.5 --                                                                         1      Foam    7.48                                     229      2,6-di-F--C.sub.6 H.sub.3 --                                                               1      Gum     7.50                                     ______________________________________                                         *Chemical shift of singlet from olefinic proton on                            β-methoxypropenoate group (ppm from tetramethylsilane). Solvent:         CDCl.sub.3 unless otherwise stated.                                      

                  TABLE III                                                       ______________________________________                                         ##STR18##                                                                    ______________________________________                                    

Table III comprises 280 compounds of the general structure above withall the values of X and n listed in Table I. That is, compounds numbers1 to 280 of Table III are the same as those of Table I except that thetriazine ring is a 3,5-disubstituted 1,2,4-triazine in Table I and a 2,4-disubstituted 1,3,5-triazine in Table III.

                  TABLE III                                                       ______________________________________                                        Compound                      Melting                                         No      X               n     Point (°C.)                                                                    Olefinic*                               ______________________________________                                         1      C.sub.6 H.sub.5 --                                                                            0     142-3   7.46                                    115     C.sub.6 H.sub.5 --                                                                            1     104-5   7.48                                    116     2-F--C.sub.6 H.sub.4 --                                                                       1      96-101 7.48                                    119     2-Cl--C.sub.6 H.sub.4 --                                                                      1     53-58   7.49                                    122     2-Br--C.sub.6 H.sub.4 --                                                                      1     52-55   7.44                                    123     2-cyano-C.sub.6 H.sub.4 --                                                                    1     Foam    7.51                                    143     2-CH.sub.3 O--C.sub.6 H.sub.4 --                                                              1     130.5-132.5                                                                           7.49                                    146     2-CH.sub.3 CH.sub.2 O--C.sub.6 H.sub.4 --                                                     1     Foam    7.48                                    175     2-CH.sub.3 --C.sub.6 H.sub.4 --                                                               1     120-1   7.48                                    178     2-C.sub.2 H.sub.5 --C.sub.6 H.sub.4 --                                                        1     Gum     7.47                                    211     3,5-di-CH.sub.3 O--C.sub.6 H.sub.3 --                                                         1     Foam    7.48                                    229     2,6-di-F--C.sub.6 H.sub.3 --                                                                  1     Gum     7.48                                    230     2- -n-C.sub.3 H.sub.7 --C.sub.6 H.sub.4 --                                                    1     66- 73  7.48                                    231     2-CF.sub.3 --C.sub.6 H.sub.4 --                                                               1     53-58   7.41                                    232     2- .sub.- i-C.sub.3 H.sub.7 --C.sub.6 H.sub.4 --                                              1     Foam    7.48                                    234     2- .sub.- i-C.sub.3 H.sub.7 O--C.sub.6 H.sub.4 --                                             1     Foam    7.47                                    242     2-[( .sub.-- E)-CH.sub.3 O.sub.2 C.C═CH.                                                  1     80-85   7.49                                            OCH.sub.3 ]--C.sub.6 H.sub.4 --                                       244     2-CH.sub.3 O-4-CH.sub.3 --C.sub.6 H.sub.3 --                                                  1     70-72   7.50                                    245     2,4-di-CH.sub.3 --C.sub.6 H.sub.3 --                                                          1     Gum     7.49                                    246     2,4,6-tri-CH.sub.3 --C.sub.6 H.sub.3 --                                                       1     74-76   7.49                                    247     2,6-di-CH.sub.3 --C.sub.6 H.sub.3 --                                                          1     62-64   7.49                                    248     2-F-6-CH.sub.3 O--C.sub.6 H.sub.3 --                                                          1     67-70   7.50                                    249     2-CH.sub.3 -4-Cl--C.sub.6 H.sub.3 --                                                          1     61-63   7.48                                    250     C.sub.6 F.sub.5 --                                                                            1     Gum     7.49                                    251     3,4-methylenedioxy-                                                                           1     Foam    7.48                                            --C.sub.6 H.sub.3 --                                                  252     3,4-di-Cl--C.sub.6 H.sub. 3 --                                                                1     Foam    7.48                                    254     3,4-di-CH.sub.3 --C.sub.6 H.sub.3 --                                                          1     Foam    7.48                                    255     2,3,5-tri-CH.sub.3 --C.sub.6 H.sub.2 --                                                       1     148.2-149.8                                                                           7.49                                    256     2,4-di-F--C.sub.6 H.sub.3 --                                                                  1     Foam    7.49                                    257     2,4-di-Cl--C.sub.6 H.sub.3 --                                                                 1     Foam    7.50                                    258     3,4,5-tri-CH.sub.3 --C.sub.6 H.sub.2 --                                                       1     Foam    7.49                                    261     2-CH.sub.3 -pyridin-3-yl                                                                      1     147-9   7.48                                    262     2-Cl-pyridin-3-yl                                                                             1     Foam    7.48                                    ______________________________________                                         *Chemical shift of singlet from olefinic proton on                            β-methoxypropenoate group (ppm from tetramethylsilane). Solvent:         CDCl.sub.3 unless otherwise stated.                                      

                  TABLE IV                                                        ______________________________________                                         ##STR19##                                                                    Compound                               Olefinic*                              No.     X             Y     n   Melting                                                                              Point (°C.)                     ______________________________________                                        1       C.sub.6 H.sub.5                                                                             Cl    1   73-75  7.47                                   2       2-cyano-C.sub.4 H.sub.4                                                                     Cl    1   138-139                                                                              7.51                                   3       2-CH.sub.3C.sub.6 H.sub.4                                                                   Cl    1   77-81  7.47                                   4       2-CH.sub.3 OC.sub.6 H.sub.4                                                                 Cl    1   57.5-65                                                                              7.48                                   5       2,6-di-FC.sub.6 H.sub.3                                                                     Cl    1   Foam   7.40                                   6       2-BrC.sub.6 H.sub.4                                                                         Cl    1   117-119                                                                              7.47                                   7       2-FC.sub.6 H.sub.4                                                                          Cl    1   48-50  7.50                                   8       2-C.sub.2 H.sub.5C.sub.6 H.sub.4                                                            Cl    1   65-70  7.46                                   9       2-NO.sub.2C.sub.6 H.sub.4                                                                   Cl    1   158- 160                                                                             7.51                                   10      2- -n-C.sub.3 H.sub.7C.sub.6 H.sub.4                                                        Cl    1   41-45  7.47                                   ______________________________________                                         *Chemical shift of singlet from olefinic proton on                            β-methoxypropenoate group (ppm from tetramethylsilane). Solvent:         CDCl.sub.3 unless otherwise stated.                                      

                                      TABLE V                                     __________________________________________________________________________     ##STR20##                                                                    Compound                       Melting                                        No.   X                    Y n Point (°C.)                                                                  Olefinic*                                __________________________________________________________________________    1     C.sub.6 H.sub.5      Cl                                                                              1 Gum   7.50                                     2     2,6-di-FC.sub.6 H.sub.4                                                                            Cl                                                                              1 Foam  7.48                                     3     2-[( .sub.--E)CH.sub.3 O.sub.2 C.CCH.OCH.sub.3 ]C.sub.6 H.sub.4                                    Cl                                                                              1 73-75 7.42, 7.52                               __________________________________________________________________________     *Chemical shift of singlet from olefinic proton on                            β-methoxypropenoate group (ppm from tetramethylsilane). Solvent:         CDCl.sub.3 unless otherwise stated.                                      

                  TABLE VI                                                        ______________________________________                                         ##STR21##                                                                    Compound                      Melting                                         No      X         Y      n    Point (°C.)                                                                     Olefinic*                              ______________________________________                                        1       C.sub.6 H.sub.5                                                                         Cl     1    Oil      7.41                                   ______________________________________                                         *Chemical shift of singlet from olefinic proton on                            β-methoxypropenoate group (ppm from tetramethylsilane). Solvent:         CDCl.sub.3 unless otherwise stated.                                      

                  TABLE VII                                                       ______________________________________                                        Selected Proton NMR Data                                                      ______________________________________                                        Table VII shows selected proton NMR data for compounds                        described in Tables I-VI. As indicated in Tables I-VI,                        chemical shifts are measured in ppm from tetramethylsilane                    and deuterochloroform was used as solvent. The NMR                            instrument operated at a frequency of 270 MHz. The                            following abbreviations are used:                                             s = singlet                                                                   d = doublet                                                                   t = triplet                                                                   q = quartet                                                                   m = multiplet                                                                 ppm = parts per million                                                       Compound No                                                                              Proton NMR data                                                    ______________________________________                                         13 (Table I)                                                                            3.56(3H, s); 3.70(3H, s); 7.28-7.45(4H, m);                                   7.48(1H, s); 7.62-7.82(3H, m);                                                8.06-8.11(1H, m); 9.11(1H, s)ppm.                                   15 (Table I)                                                                            3.51(3H, s); 3.64(3H, s); 7.32-7.48(5H, m,                                    including 1H singlet at 7.42); 8.25-8.29                                      (2H, d); 8.35-8.39(2H, d); 9.53(1H, s)ppm.                         242 (Table I)                                                                            3.55(3H, s); 3.60(3H, s); 3.70(3H, s);                                        3.72(3H, s); 7.17-7.41(8H, m); 7.43(1H, s);                                   7.49(1H, s); 8.64(1H, s)ppm.                                        1 (Table II)                                                                            3.61(3H, s); 3.72(3H, s); 7.11-7.45(9H, m);                                   7.48(1H, s); 8.71(1H, s)ppm.                                       123 (Table III)                                                                          3.64(3H, s); 3.73(3H, s); 7.10-7.48(6H, m);                                   7.51(1H, s); 7.59-7.77(2H, m); 8.67(1H, s)                                    ppm.                                                               146 (Table III)                                                                          1.25(3H, t); 3.61(3H, s); 3.73(3H, s);                                        4.03(2H, q); 6.94-7.03(2H, m);                                                7.12-7.40(6H, m); 7.48(1H, s); 8.61(1H, s)                                    ppm.                                                               178 (Table III)                                                                          1.18(3H, t); 2.55(2H, q); 3.62(3H, s);                                        3.73(3H, s); 7.02-7.12(1H, m); 7.18-                                          7.42(8H, m); 7.47(1H, s); 8.62(1H, s)ppm.                          229 (Table III)                                                                          3.60(3H, s); 3.70(3H, s); 6.94-7.08(2H, t);                                   7.13-7.44(5H, m); 7.48(1H, s); 8.67(1H, s)                                    ppm.                                                               232 (Table III)                                                                          1.19(6H, d); 3.04(1H, septet); 3.61(3H, s);                                   3.74(3H, s); 7.01-7.09(1H, m); 7.18-                                          7.41(7H, m); 7.48(1H, s); 8.63(1H, s)ppm.                          234 (Table III)                                                                          1.21(6H, d); 3.62(3H, s); 3.73(3H, s);                                        4.52(1H, septet); 6.94-7.04(2H, m);                                           7.12-7.40(6H, m); 7.47(1H, s); 8.61(1H, s)                                    ppm.                                                               241 (Table III)                                                                          2.35(3H, s); 3.60(3H, s); 3.74(3H, s);                                        3.76(3H, s); 6.80(2H, d); 7.01(1H, d);                                        7.30(4H, m); 7.50(1H, s); 8.60(1H, s)ppm.                          245 (Table III)                                                                          2.14(3H, s); 2.32(3H, s); 3.60(3H, s);                                        3.75(3H, s); 6.95(1H, d); 7.05(2H, m);                                        7.30(4H, m); 7.49(1H, s); 8.60(1H, s)ppm.                          246 (Table III)                                                                          2.10(6H, s); 2.30(3H, s); 3.60(3H, s);                                        3.74(3H, s); 6.90(2H, s); 7.30(4H, m);                                        7.49(1H, s); 8.60(1H, s)ppm.                                       247 (Table III)                                                                          2.13(6H, s); 3.60(3H, s); 3.73(3H, s);                                        7.10(3H, s); 7.30(4H, m); 7.49(1H, s);                                        8.60(1H, s)ppm.                                                    248 (Table III)                                                                          3.60(3H, s); 3.70(3H, s); 3.80(3H, s);                                        6.80(2H, m); 7.30(5H, m); 7.50(1H, s);                                        8.63(1H, s)ppm.                                                    249 (Table III)                                                                          2.15(3H, s); 3.60(3H, s); 3.73(3H, s);                                        7.01(1H, d); 7.30(6H, m); 7.48(1H, s);                                        8.62(1H, s)ppm.                                                    250 (Table III)                                                                          3.60(3H, s); 3.70(3H, s); 7.30(3H, m);                                        7.20(1H, d); 7.49(1H, s); 8.70(1H, s)ppm.                          251 (Table III)                                                                          3.60(3H, s); 3.75(3H, s); 6.00(2H, s);                                        6.60(2H, m); 6.80(1H, d); 7.30(4H, m);                                        7.48(1H, s); 8.65(1H, s)ppm.                                       252 (Table III)                                                                          3.60(3H, s); 3.75(3H, s); 7.05(1H, dd);                                       7.20(1H, d); 7.35(4H, m); 7.45(1H, d);                                        7.48(1H, s); 8.65(1H, s)ppm.                                       253 (Table III)                                                                          3.62(3H, s); 3.74(3H, s); 3.76(6H, s);                                        6.33(2H, d); 6.40(1H, d); 7.35(4H, m);                                        7.48(1H, s); 8.65(1H, s)ppm.                                       254 (Table III)                                                                          2.25(6H, s); 3.60(3H, s); 3.75(3H, s);                                        6.90(2H, m); 7.15(1H, m); 7.35(4H, m);                                        7.48(1H, s); 8.62(1H, s)ppm.                                       255 (Table III)                                                                          2.00(3H, s); 2.27(3H, s); 2.29(3H, s);                                        3.60(3H, s); 3.73(3H, s); 6.75(1H, d);                                        6.92(1H, s); 7.25(1H, d); 7.35(3H, m);                                        7.49(1H, s); 8.60(1H, s)ppm.                                       256 (Table III)                                                                          3.60(3H, s); 3.72(3H, s); 6.95(2H, m);                                        7.20(1H, m); 7.35(4H, m); 7.49(1H, s);                                        8.65(1H, s)ppm.                                                    257 (Table III)                                                                          3.60(3H, s); 3.75(3H, s); 7.30(6H, m);                                        7.49(1H, s); 7.50(1H, s); 8.65(1H, s)ppm.                          258 (Table III)                                                                          2.15(3H, s); 2.30(6H, s); 3.62(3H, s);                                        3.75(3H, s); 6.80(2H, s); 7.30(4H, m);                                        7.49(1H, s); 8.62(1H, s)ppm.                                       262 (Table III)                                                                          3.63(3H, s); 3.74(3H, s); 7.17-7.42(6H, m);                                   7.48(1H, s); 7.59(1H, dd); 8.33-8.38(1H, m);                                  8.67(1H, s)ppm.                                                     5 (Table IV)                                                                            3.63(3H, s); 3.73(3H, s); 6.94-7.14(2H, m);                                   7.15-7.38(3H, m); 7.40(1H, s)ppm.                                   1 (Table V)                                                                             3.66(3H, s); 3.78(3H, s); 7.09-7.42(9H, m);                                   7.50(1H, s)ppm.                                                     2 (Table V)                                                                             3.62(3H, s); 3.72(3H, s); 6.90-7.10(2H, m);                                   7.10-7.50(5H, m); 7.50(1H, s); 8.78(1H, s)                                    ppm.                                                               ______________________________________                                    

The compounds of the invention of formula (I) [equivalent to (IA) when Wis the group CH₃ O₂ C.C═CH.OCH₃ ] can be prepared by the steps shown inSchemes I, II and III. In these Schemes X¹ is an optionally substitutedaromatic or heteroaromatic ring or a group which can be converted intosuch a ring; W is CH₃ O₂ C.C═CH.OCH₃ or a group that can be transformedinto CH₃ O₂ C.C.═CH.OCH₃ using methods previously described such as inEP-A-0242081; Z¹ and Z² (which may be the same or different) are leavinggroups (such as halogen or CH₃ SO₂ -), Z¹ being the leaving group whichis more readily displaced if (a) both Z¹ and Z² are present in the samecompound or (b) if Z¹ and Z² are both present in different compounds ofa coupling reaction; T is hydrogen or a metal (such as sodium) and anytwo of K, L and M are nitrogen and the other is CY (or a group that canbe converted into CY, such as C-halogen which can be converted into CH).The reactions shown in Schemes I-III are performed either in a suitablesolvent or without a solvent, and at a suitable temperature.

Thus compounds of the invention of formula (IA, n=0) can be prepared bytreatment of substituted triazines of general formula (III) with phenolsof formula (II) (wherein W is as defined above and T is hydrogen) in thepresence of a base (such as potassium carbonate) (Scheme I).

Alternatively, compounds of formula (IA, n=b 0) can be prepared bytreatment of substituted triazines of general formula (III) withphenolate salts of formula (II) (wherein W is as defined above and T isa metal, such as sodium). ##STR22## Compounds of the invention offormula [(IA, n=1): W is the group CH₃ O₂ C.C═CH.OCH₃ ] can be preparedby two successive reactions of the Ullmann type, using appropriatelyfunctionalised benzene and triazine intermediates. The pathways shown inSchemes II and III illustrate that the order of the steps by which thesebenzene and triazine units are assembled can be varied.

For example, compounds of formula (IA, n=1) can be prepared fromcompounds of formula (IV) by treatment with phenols of formula (V),wherein T is hydrogen, in the presence of a base (such as potassiumcarbonate). Alternatively, compounds of formula (IA, n=1) can beprepared from compounds of formula (IV) by treatment with phenolatesalts of formula (V), wherein T is a metal (such as sodium) (Scheme II).

Compounds of formula (IV) can be prepared by treatment of compounds offormula (VI) with phenols of formula (II), wherein T is hydrogen, in thepresence of a base (such as potassium carbonate). Alternatively,compounds of formula (IV) can be prepared by treatment of compounds offormula (VI) with phenolate salts of formula (II), wherein T is a metal(such as sodium).

Compounds of formula (IA, n=1) can also be prepared by treatment ofcompounds of formula (VII) with phenols of formula (II), wherein T ishydrogen, in the presence of a base (such as potassium carbonate).Alternatively, compounds of formula (IA, n=1) can be prepared bytreatment of compounds of formula (VII) with phenolate salts of formula(II), wherein T is a metal (such as sodium) (Scheme III).

Compounds of formula (VII) can be prepared by treatment of triazines offormula (VIII) with compounds of formula (V), wherein T is hydrogen, inthe presence of a base (such as potassium carbonate). Alternatively,compounds of formula (VII) can be prepared by treatment of triazines offormula (VIII) with compounds of formula (V), wherein T is a metal (suchas sodium).

In some instances it is advantageous to use intermediates (IV) whereinZ² is the group 2-W-C₆ H₄ O, this group functioning as the leaving groupon reaction with the compound (V). These intermediates (IV) wherein Z²is 2-W-C₆ H₄ O may be prepared by treatment of triazines (VI) with anexcess of compound (II). Similarly, intermediates (VII) in which Z² isX¹ O may be used, the group X¹ O functioning as the leaving group onreaction with the phenol or phenolate (II). These intermediates (VII)wherein Z² is X¹ O may be prepared by treatment of triazines (VIII) withan excess of compound (V). ##STR23##

The last stage of the synthesis of the compounds of the invention maytherefore be one of the following:

(i) construction of the group CH₃ O₂ C.C.═OCH₃ [in which case the groupW in the compounds (II) and (IA) represents an appropriate precursor tothe group CH₃ O₂ C.C═OCH₃ during the coupling reaction shown in SchemeI]; or

(ii) the final coupling reactions shown in Schemes I-III [in which casethe group W in the intermediate (II) represents the group CH₃ O₂C.C═CH.OCH₃ ]; or

(iii) modification to the group X¹, either to convert it into anaromatic or heteroaromatic ring or, if it is already such a ring, tomodify a substituent on it; or

(iv) removal of a substituent (such as halogen) from the triazine ringof (IA) to afford a triazine wherein any two of K, L and M are nitrogenand the other is CH.

Triazines of formulae (III), (VI) and (VIII) and compounds of formula(V) can be prepared by standard methods described in the chemicalliterature. Compounds of formula (II) can either be prepared by standardmethods described in the chemical literature, or when W is CH₃ O₂C.C═OCH₃ can be prepared by methods described in EP-A-0242081.

In a further aspect, the invention provides processes as hereindescribed for preparing the compounds of the invention.

The compounds of the invention are active fungicides and may be used tocontrol one or more of the following pathogens:

Pyricularia oryzae on rice.

Puccinia recondita, Puccinia striiformis and other rusts on wheat,Puccinia hordei, Puccinia striiformis and other rusts on barley, andrusts on other hosts e.g. coffee, pears, apples, peanuts, vegetables andornamental plants.

Erysiphe graminis (powdery mildew) on barley and wheat and other powderymildews on various hosts such as

Sphaerotheca macularis on hops, Sphaerotheca fuliginea on cucurbits(e.g. cucumber), Podosphaera leucotricha on apple and Uncinula necatoron vines.

Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pyrenophoraspp., Pseudocercosporella herpotrichoides and Gaeumannomyces graminis oncereals.

Cercospora arachidicola and Cercosporidium personata on peanuts andother Cercospora species on other hosts, for example, sugar beet,bananas, soya beans and rice.

Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables,vines and other hosts.

Alternaria spp. on vegetables (e.g. cucumber), oil-seed rape, apples,tomatoes and other hosts.

Venturia inaequalis (scab) on apples.

Plasmopara viticola on vines.

Other downy mildews such as Bremia lactucae on lettuce, Peronospora spp.on soybeans, tobacco, onions and other hosts, Pseudoperonospora humulion hops and Pseudoperonospora cubensis on cucurbits.

Phytophthora infestans on potatoes and tomatoes and other Phytophthoraspp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco,cocoa and other hosts.

Thanatephorus cucumeris on rice and other Rhizoctonia species on varioushosts such as wheat and barley, vegetables, cotton and turf.

Some of the compounds show a broad range of activities against fungi invitro. They may also have activity against various post-harvest diseasesof fruit (e.g. Penicillium digitatum and italicum and Trichoderma virideon oranges, Gloeosporium musarum on bananas and Botrytis cinerea ongrapes).

Further, some of the compounds may be active as seed dressings againstFusarium spp., Septoria spp., Tilletia spp., (bunt, a seed-borne diseaseof wheat), Ustilago spp. and Helminthosporium spp. on cereals,Rhizoctonia solani on cotton and Pyricularia oryzae on rice.

The compounds may move acropetally/locally in plant tissue. Moreover,the compounds may be volatile enough to be active in the vapour phaseagainst fungi on the plant.

The invention therefore provides a method of combating fungi whichcomprises applying to a plant, to a seed of a plant or to the locus ofthe plant or seed a fungicidally effective amount of a compound ashereinbefore defined, or a composition containing the same.

The compounds may be used directly for agricultural purposes but aremore conveniently formulated into compositions using a carrier ordiluent. The invention thus provides fungicidal compositions comprisinga compound as hereinbefore defined and an acceptable carrier or diluenttherefor.

The compounds can be applied in a number of ways. For example, they canbe applied, formulated or unformulated, directly to the foliage of aplant, to seeds or to other medium in which plants are growing or are tobe planted, or they can be sprayed on, dusted on or applied as a creamor paste formulation, or they can be applied as a vapour or as slowrelease granules.

Application can be to any part of the plant including the foliage,stems, branches or roots, or to soil surrounding the roots, or to theseed before it is planted, or to the soil generally, to paddy water orto hydroponic culture systems. The invention compounds may also beinjected into plants or sprayed onto vegetation using electrodynamicspraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatments.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granulescomprising the active ingredient (invention compound) and a soliddiluent or carrier, for example, fillers such as kaolin, bentonite,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,fuller's earth, gypsum, diatomaceous earth and china clay. Such granulescan be preformed granules suitable for application to the soil withoutfurther treatment. These granules can be made either by impregnatingpellets of filler with the active ingredient or by pelleting a mixtureof the active ingredient and powdered filler. Compositions for dressingseed may include an agent (for example, a mineral oil) for assisting theadhesion of the composition to the seed: alternatively the activeingredient can be formulated for seed dressing purposes using an organicsolvent (for example, N-methylpyrrolidone, propylene glycol ordimethylformamide). The compositions may also be in the form of wettablepowders or water dispersible granules comprising wetting or dispersingagents to facilitate the dispersion in liquids. The powders and granulesmay also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving theactive ingredient in an organic solvent optionally containing a wettingor emulsifying agent and then adding the mixture to water which may alsocontain a wetting or emulsifying agent. Suitable organic solvents arearomatic solvents such as alkylbenzenes and alkylnaphthalenes, ketonessuch as isophorone, cyclohexanone, and methylcyclohexanone, chlorinatedhydrocarbons such as chlorobenzene and trichlorethane, and alcohols suchas benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared byball or bead milling with a dispersing agent with a suspending agentincluded to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols whereinthe formulation is held in a container under pressure of a propellant,e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating in enclosed spacesa smoke containing the compounds.

Alternatively, the compounds may be used in micro-encapsulated form.They may also be formulated in biodegradable polymeric formulations toobtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The invention compounds can be used as mixtures with fertilisers (e.g.nitrogen-, potassium- or phosphorus-containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the compound are preferred. Such granules suitablycontain up to 25% by weight of the compound. The invention thereforealso provides a fertiliser composition comprising a fertiliser and thecompound of general formula (I) or a salt or metal complex thereof.

Wettable powders, emulsifiable concentrates and suspension concentrateswill normally contain surfactants, e.g. a wetting agent, dispersingagent, emulsifying agent or suspending agent. These agents can becationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for example,cetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphuric acid (for example, sodium laurylsulphate), and salts of sulphonated aromatic compounds (for example,sodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropyl- naphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonylphenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example, polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and swelling clays such as bentonite orattapulgite.

Compositions for use as aqueous dispersions or emulsions are generallysupplied in the form of a concentrate containing a high proportion ofthe active ingredient, the concentrate being diluted with water beforeuse. These concentrates should preferably be able to withstand storagefor prolonged periods and after such storage be capable of dilution withwater in order to form aqueous preparations which remain homogeneous fora sufficient time to enable them to be applied by conventional sprayequipment. The concentrates may conveniently contain up to 95%, suitably10-85%, for example 25-60%, by weight of the active ingredient. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient may be used.

The compositions of this invention may contain other compounds havingbiological activity, e.g. compounds having similar or complementaryfungicidal activity or which possess plant growth regulating, herbicidalor insecticidal activity.

A fungicidal compound which may be present in the composition of theinvention may be one which is capable of combating ear diseases ofcereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporiumspp., seed and soil-borne diseases and downy and powdery mildews ongrapes and powdery mildew and scab on apple, etc. By including anotherfungicide, the composition can have a broader spectrum of activity thanthe compound of general formula (I) alone. Further the other fungicidecan have a synergistic effect on the fungicidal activity of the compoundof general formula (I). Examples of fungicidal compounds which may beincluded in the composition of the invention are(RS)-1-aminopropylphosphonic acid,(RS)-4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazol-1-yl-methyl)butyronitrile,(Z)-N-but-2-enyloxymethyl-2-chloro-2',6'-diethylacetanilide,1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea,1-[(2RS,4RS;2RS,4RS)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofurfuryl]-1H-1,2,4-triazole,3-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-quinazolin-4(3H)-one,3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-methyl)-1,3-dioxolan-2-yl]phenyl-4-chlorophenylether, 3-chloro-5-ethylsulphinylthiophene-2,4-dicarbonitrile,4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenz-imidazole-1-sulphonamide,5-ethyl-5,8-dihydro-8-oxo(1,3)-dioxolo(4,5-g)quinoline-7-carboxylicacid, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone,anilazine, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol,blasticidin S, bupirimate, buthiobate, captafol, captan, carbendazim,carboxin, chlorbenzthiazone, chloroneb, chlorothalonil, chlorozolinate,copper containing compounds such as copper oxychloride, copper sulphateand Bordeaux mixture, cycloheximide, cymoxanil, cyproconazole,cyprofuram, di-2-pyridyl disulphide 1,1'-dioxide, dichlofluanid,dichlone, diclobutrazol, diclomezine, dicloran, difenoconazole,dimethamorph, dimethirimol, diniconazole, dinocap, ditalimfos,dithianon, dodemorph, dodine, edifenphos, etaconazole, ethirimol, ethyl(Z)-N-benzyl-N-([methyl-(methylthioethylideneamino-oxycarbonyl)amino]-thio)-β-alaninate,etridiazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol,fluzilazole, folpet, fosetyl-aluminium, fuberidazole, furalaxyl,furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, imazalil,imibenconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin,mancozeb, maneb, mepronil, metalaxyl, methfuroxam, metsulfovax,myclobutanil, N-(4-methyl-6-prop-1-ynylpyrimidin-2-yl)-aniline,neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl,nuarimol, ofurace, organomercury compounds, oxadixyl, oxycarboxin,pefurazoate, penconazole, pencycuron, phenazin oxide, phthalide,polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb,propiconazole, propineb, prothiocarb, pyrazophos, pyrifenox, pyroquilon,pyroxyfur, pyrrolnitrin, quinomethionate, quintozene, streptomycin,sulphur, techlofthalam, tecnazene, tebuconazole, tetraconazole,thiabendazole, thiophanate-methyl, thiram, tolclofos-methyl, triacetatesalt of 1,1,'-iminodi(octamethylene)diguanidine, triadimefon,triadimenol, triazbutyl, tricyclazole, tridemorph, triforine,validamycin A, vinclozolin, zarilamid and zineb. The compounds ofgeneral formula (I) can be mixed with soil, peat or other rooting mediafor the protection of plants against seed-borne, soil-borne or foliarfungal diseases.

Suitable insecticides which may be incorporated in the composition ofthe invention include buprofezin, carbaryl, carbofuran, carbosulfan,chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinon, dimethoate,ethofenprox, fenitrothion, fenobucarb, fenthion, formothion, isoprocarb,isoxathion, monocrotophos, phenthoate, pirimicarb, propaphos and XMC.

Plant growth regulating compounds are compounds which control weeds orseedhead, formation, or selectively control the growth of less desirableplants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with theinvention compounds are 3,6-dichloropicolinic acid,1-(4-chlorophenyl)-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, methyl-3,6-dichloroanisate, abscisic acid, asulam,benzoylprop-ethyl, carbetamide, daminozide, difenzoquat, dikegulac,ethephon, fenpentezol, fluoridamid, glyphosate, glyphosine,hydroxybenzonitriles (e.g. bromoxynil), inabenfide, isopyrimol, longchain fatty alcohols and acids, maleic hydrazide, mefluidide,morphactins (e.g. chlorfluoroecol), paclobutrazol, phenoxyacetic acids(e.g. 2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoicacid), substituted quaternary ammonium and phosphonium compounds (e.g.chloromequat, chlorphonium or mepiquatchloride), tecnazene, the auxins(e.g. indoleacetic acid, indolebutyric acid, naphthylacetic acid ornaphthoxyacetic acid), the cytokinins (e.g. benzimidazole,benzyladenine, benzylaminopurine, diphenylurea or kinetin), thegibberellins (e.g. GA₃, GA₄ or GA₇) and triapenthenol.

The following Examples illustrate the invention. In the Examples, theterm `ether` refers to diethyl ether, anhydrous magnesium sulphate wasused to dry solutions, and solutions were concentrated under reducedpressure. Reactions involving air- or water-sensitive intermediates wereperformed under an atmosphere of nitrogen and solvents were dried beforeuse, where appropriate. Unless otherwise stated, chromatography wasperformed on a column of silica gel as the stationary phase. NMR dataare selective; no attempt is made to list every absorption in all cases.¹ H NMR spectra were recorded using CDCl₃ -solutions. The followingabbreviations are used:

DMSO=dimethylsulphoxide

DMF=N,N-dimethylformamide

NMR=nuclear magnetic resonance

IR=infrared

GC=Gas chromatography

s=singlet

d=doublet

m=multiplet

mp=melting point

ppm=parts per million

EXAMPLE 1

This Example illustrates the preparation of (E)-methyl2-[2-(5-(4-chlorophenyl)-1,2,4-triazin-3-yloxy)phenyl]-3-methoxypropenoate(Compound No. 7 of Table I).

To a stirred solution of (E)-methyl2-(2-hydroxyphenyl)-3-methoxypropenoate (0.44 g, 2.1 mmol; prepared asdescribed in Example 3 of EP-A-0242081) and anhydrous potassiumcarbonate (0.276 g, 2.0 mmol) in dry DMF (5 ml) at 0°-2° C. undernitrogen was added drop-wise over 10 minutes a solution of5-(4-chlorophenyl)-3-methylsulphonyl-1,2,4-triazine (0.54 g, 2.0 mmol;prepared as described by E. C. Taylor, J. E. Macor and J. L. Pont inTetrahedron, 1987, 43, 5145) in dry DMF (5 ml). The reaction mixture wasstirred for 15 minutes and then allowed to warm to ambient temperature.After 1 hour, a further amount of the sulphone (0.11 g) was added. Thereaction mixture was then stirred at ambient temperature for 1 hour,poured into water and extracted into ether (×3). The combined yellowether extracts were washed with dilute sodium hydroxide solution (×3)and water (×3) and then dried. The ether was removed under reducedpressure to give a yellow solid (0.46 g). Trituration with ether andfiltration afforded the title compound as a pale yellow solid (0.374 g);m.p. 140°-2° C.; IR maxima 1721, 1621 cm⁻¹ ; ¹ H NMR (CDCl₃)δ3.51(3H,s); 3.71(3H,s); 7.29-7.47 (5H,m, including a 1H singlet at7.43); 7.48-7.52(2H,d); 8.02-8.06 (2H,d); 9.03(1H,s)ppm.

EXAMPLE 2

This Example illustrates the preparation of (E)-methyl2-[2-(4-phenyl-1,3,5-triazin-2-yloxy)phenyl]-3-methoxypropenoate(Compound No. 1 of Table III).

To a stirred solution of (E)-methyl2-(2-hydroxyphenyl)-3-methoxypropenoate (0.458 g, 2.2 mmol; prepared asdescribed in Example 3 of EP-A-0242081) and anhydrous potassiumcarbonate (276 mg, 2.0 mmol) in dry DMF (5 ml) at 0°-2° C. undernitrogen was added drop-wise over 5 minutes a solution of2-chloro-4-phenyl-1,3,5-triazine (383 mg, 2.0 mmol; prepared asdescribed by R. L. N. Harris in Synthesis, 1980, 841) in dry DMF (5 ml).The reaction mixture was stirred for 3.75 hours and then allowed to warmto ambient temperature. Water was added and the white precipitate whichformed was extracted into ethyl acetate (×3). The combined organicextracts were washed with dilute sodium hydroxide solution (×2) andwater (×3) and then dried. The ether was removed under reduced pressureto give a sticky, pale yellow solid. Trituration with petrol followed byfiltration then afforded the title compound as a cream-coloured solid(0.49 g); m.p. 142°-3° C.; IR maxima 1710, 1631 cm⁻¹ ; ¹ H NMR (CDCl₃) δ3.55(3H,s); 3.68(3H,s); 7.28-7.62(8H,m, including a 1H singlet at 7.46);8.40-8.44(2H,d); 8.95 (1H,s)ppm.

EXAMPLE 3

This Example illustrates the preparation of (E)-methyl2-[2-(4-phenoxy-1,3,5-triazin-2-yloxy)-phenyl]-3-methoxypropenoate(Compound No. 115 of Table III).

A mixture containing (E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate(2.58 g, 12.40 mmol), 2,4-dichloro-6-phenoxy-1,3,5-triazine (3.00 g,12.40 mmol), anhydrous potassium carbonate (1.71 g, 12.40 mmol) and 4 Åmolecular sieves in dry THF (60 ml) was stirred at room temperature fortwo days. The cloudy reaction mixture was diluted with water (50 ml) andthen extracted with dichloromethane (2×60 ml) (an emulsion formed whichwas dispersed by filtration through celite). The combined organicextracts were dried and evaporated to give a pale yellow oil (5.68 g).Chromatography (eluent ether-n-hexane, 1:1) afforded a white foam (3.79g) which was recrystallised from ether-n-hexane at low temperature togive (E)-methyl2-[2-(4-chloro-6-phenoxy-1,3,5-triazin-2-yloxy)phenyl]-3-methoxypropenoateas a white powder (3.10 g, 60%); m.p. 103°-4° C.

(E)-Methyl2-[2-(4-chloro-6-phenoxy-1,3,5-triazin-2-yloxy)phenyl]-3-methoxypropenoate(2.00 g, 4.84 mmol) was stirred at room temperature over the weekendwith sodium hypophosphite (NaH₂ PO₂, 1.28 g, 14.51 mmol), potassiumcarbonate (2.30 g, 16.66 mmol) and 5% palladium on carbon (0.30 g) inTHF (45 ml) and water (15 ml). The reaction mixture was filtered throughcelite which was washed well with dichloromethane and water. The organiclayer was separated, and the aqueous layer further extracted withdichloromethane. The combined organic layers were dried and evaporatedto give a colourless oil (1.79 g). Chromatography (eluentether-n-hexane, 2:1) gave a white solid (0.88 g) which onrecrystallisation from ether (containing a trace of dichloromethane) andn-hexane afforded the title compound as a white powder (0.78 g, 43%);m.p. 104°-5° C.; IR maxima 1694, 1638 cm⁻¹ ; mass spectrum m/e 379 (M⁺);¹ H NMR (CDCl₃) δ 3.63(3H,s); 3.75(3H,s); 7.13-7.50(9H,m); 7.48(1H,s ;and 8.64(1H,s) ppm.

EXAMPLE 4

This Example illustrates the preparation of (E)-methyl2-[2-(4-(2-bromophenoxy)-1,3,5-triazin-2-yloxy)phenyl]-3-methoxypropenoate(Compound No. 122 of Table III).

To a stirred solution of 2,6-dichloro-1,3,5-triazine (0.3 g, 2 mmol;made according to R L N Harris, Synthesis, 1981, 907) and potassiumcarbonate (0.28 g, 2 mmol) in dry acetonitrile (25 ml) at 0° C. under anatmosphere of nitrogen was added dropwise a solution of (E)-methyl2-(2-hydroxyphenyl)-3-methoxypropenoate (0.42 g, 2 mmol) in dryacetonitrile (7 ml). Anhydrous caesium fluoride (0.30 g, 2 mmol) and acatalytic amount of 18-crown-6 were added with stirring and thetemperature was allowed to rise to room temperature. After stirringovernight, the reaction mixture was filtered and evaporated to leave ayellow/orange paste. Chromatography (eluent diethyl ether) afforded(E)-methyl2-[2-(4-chloro-1,3,5-triazin-2-yloxy)phenyl]-3-methoxypropenoate (0.42g) as a white solid, m.p. 137°-140° C.; Infrared max. 1704, 1631 cm⁻¹ ;¹ H NMR (CDCl₃) δ 3.63(3 H,s); 3.75(3H,s); 7.19-7.29(1H,m);7.31-7.45(3H,m); 7.47(1H,s); 8.74(1H,s) ppm.

2-Bromophenol (0.14 g, 0.787 mmol) and potassium carbonate (0.11 g,0.787 mmol) were heated together in dry DMF (20 ml) under nitrogen for15 minutes. A solution of (E)-methyl2-[2-(4-chloro-1,3,5-triazin-2-yloxy)phenyl]-3-methoxypropenoate (0.23g, 0.712 mmol) in DMF and a catalytic amount of copper(I) chloride wereadded and the resulting mixture stirred at 60° C. for 2 hours. Thereaction mixture was poured into water and then extracted with ether(×3). The combined ether extracts were washed with brine, dilute aqueoussodium hydroxide solution (×2) and water (×3) and then dried.Evaporation of the solvent gave a yellow gum (0.22 g) which waschromatographed (eluent diethyl ether) to afford the title compound as awhite powder (0.13 g); m.p. 52°-55° C.; Infrared max. 1709, 632 cm⁻¹ ; ¹H NMR (CDCl₃) δ 3.63(3H,s ; 3.74(3H,s); 7.14-7.44(7H,m); 7.48(1H,s);7.66(1H,dd); 8.65(1H,s) ppm.

EXAMPLE 5

This Example illustrates the preparation of (E)-methyl2-[2-(4,6-dichloro-1,3,5-triazin-2-yloxy)phenyl]-3-methoxypropenoate, anintermediate for the synthesis of compounds of the invention.

To a stirred mixture containing cyanuric chloride (1.85 g, 10 mmol),potassium carbonate (1.38 g, 10 mmol) and molecular sieves in dry THF(40 ml) at room temperature was added a solution of (E)-methyl2-(2-hydroxyphenyl)-3-methoxypropenoate (2.08 g, 10 mmol) in dry THF (7ml). After stirring overnight, some water was added and the molecularsieves were removed by filtration. After stirring overnight again, thereaction mixture was added dropwise to another equivalent of cyanuricchloride and potassium carbonate in THF and then stirred overnight. Thereaction mixture was filtered, diluted with water and then extractedthoroughly with ethyl acetate. The combined extracts were dried andevaporated to give a yellow gum (2.02 g). Chromatography gave the titlecompound as a yellow powder (200 mg); ¹ H NMR (CDCl₃) δ 3.65(3H,s);3.77(3H,s); 7.18-7.29(1H,m); 7.31-7.46(3H,m); 7.48(1H,s) ppm; massspectrum m/e 355 (M⁺), 324, 296.

EXAMPLE 6

This Example illustrates the preparation of (E)-methyl2-[2-(6-chloro-3-phenoxy-1,2,4-triazin-5-yloxy)phenyl]-3-methoxypropenoate(Compound No. 1 of Table V).

To a stirred suspension of sodium hydride (0.99 g, 11.38 mmol, 55%dispersion in oil pre-washed with dry THF) in dry THF (10 ml) undernitrogen was added phenol (2.13 g, 22.76 mmol, freshly distilled). Whenall effervescence had ceased, the slightly cloudy solution was addeddropwise to a stirred solution of 3,5,6-trichloro-1,2,4-triazine (2.10g, 11.38 mmol, prepared according to B A Loving et al., J. Het. Chem.,1971, 8, (1095-6) in dry THF (25 ml) under nitrogen. An exothermicreaction took place which gave rise to a yellow solution with a whiteprecipitate. After 90 minutes at room temperature, the reaction mixturewas filtered and evaporated to give a yellow oil (4.24 g). The oil wastriturated with diethyl ether-dichloromethane to afford a creamcoloured, sticky solid (0.79 g). The trituration filtrate was evaporatedto leave a pale yellow oil (3.30 g). Chromatography of this oil (eluentethyl acetate-n-hexane-acetic acid, 1:10:0.1) gave3,5-diphenoxy-6-chloro-1,2,4-triazine as a colourless oil (1.92 g) whichcrystallised from ether-n-hexane as a white solid (1.38 g, 40.5% yield)m.p. 63°-4° C.

To a stirred solution of 3,5-diphenoxy-6-chloro-1,2,4-triazine (0.60 g,2.00 mmol) in dry THF (12 ml) at 0° C. under an atmosphere of nitrogenwere added potassium carbonate (0.55 g, 4.00 mmol) and some molecularsieves. To the resulting mixture was added dropwise a solution of(E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate (0.83 g, 4.00 mmol)in dry THF (8 ml). The temperature was allowed to reach room temperatureand stirring continued overnight. The reaction mixture was cooled to 0°C. and methyl iodide (1.14 g, 8.00 mmol) and potassium carbonate (0.55g, 4.00 mmol) were added. The reaction mixture was allowed slowly towarm to room temperature and then stirred over the weekend. The reactionmixture was then diluted with dichloromethane (25 ml), filtered and thenwashed with water (2+20 ml). The organic layer was dried and evaporatedto give a light brown oil (1.73 g). Repeated chromatography (eluentethyl acetate, n-hexane, acetic acid mixtures) afforded the titlecompound as a thick oil (0.28 g, 34%); ¹ H NMR δ 3.66(3H,s); 3.78(3H,s);7.09-7.42(9H,m); 7.50(1H,s) ppm; Infrared max. 1707, 1631 cm⁻¹, massspectrum m/e 413 (M⁺).

EXAMPLE 7

This Example illustrates the preparation of (E)-methyl2-[2-(3-phenoxy-1,2,4-triazinyloxy)phenyl]-3-methoxypropenoate (compoundNo 1 of Table II).

To a stirred solution of (E)-methyl2-[2-(6-chloro-3-phenoxy-1,2,4-triazin-5-yloxy)phenyl]-3-methoxypropenoate(0.1 g, 0.24mmol prepared as in Example 6) in THF (4 ml) containingpotassium carbonate (0.116 g, 0.84 mmol) and 5% palladium on carbon (20mg) was added dropwise a solution of sodium hypophosphite (0.0638 g,0.72 mmol) in water (1 ml). After stirring overnight, a second batch ofeach reagent was added and stirring continued overnight. A third batchof each reagent was then added and stirring continued over the weekend.Hydrogen gas was then bubbled through the reaction mixture for 51/2hours. The reaction mixture was partitioned between water (5 ml) anddichloromethane (15 ml) and filtered. The dichloromethane layer wasseparated and the aqueous layer was extracted further withdichloromethane (2×10 ml). The combined organic extracts were dried,filtered and evaporated to give a thick, light brown oil (50 mg).Chromatography on silica (eluent ether-n-hexane,3:1) afforded the titlecompound as a white foam (25 mg, 27%); ¹ H NMR (CDCl₃) δ 3.61(3H,s);3.72 (3H,s); 7.11-7.45 (9H,m); 7.48(1H,s) 8.71(1H,s); Infrared max.1707, 1631cm⁻¹.

EXAMPLE 8

This Example illustrates the preparation of: ##STR24##

To a stirred solution of (E)-methyl2-(2-hydroxyphenyl)-3-methoxypropenoate (4.16 g, 20 mmol) in dry THFcontaining 4A molecular sieves (5 ml) and potassium carbonate (2.76 g,20 mmol) under nitrogen at 0° C. was added dropwise over 15 minutes asolution of 3,5,6-trichloro-1,2,4-triazine (3.69 g, 20 mmol) in THF (25ml). The reaction mixture was stirred at 0° C. for 30 minutes and thenallowed to warm to room temperature overnight. The reaction mixture wasdiluted with dichloromethane, filtered and evaporated to give an orangegum (7.58 g). Chromatography (eluent diethyl ether-n-hexane, 1:1) gave(E)-methyl2-[2-(3,6-dichloro-1,2,4-triazin-5-yloxy)-phenyl]-3-methoxypropenoate(5,90 g, 83%) as a cream coloured solid; m.p. 140°-2° C., Infrared max.1696, 1624cm⁻¹ ; ¹ H NMR (CDCl₃) δ 63.65(3H,s); 3.78 (3H,s);7.26-7.49(4H,m); 7.47 (1H,s) ppm.

To a stirred mixture of (E)-methyl2-[2-(3,6-dichloro-1,2,4-triazin-5-yloxy)phenyl]-3-methoxypropenoate(0.30 g, 0.84 mmol) and potassium carbonate (0.12 g, 0.84 mmol) in dryacetonitrile (7 ml) at room temperature under nitrogen was added asolution of (E)-methyl 2-(2-hydroxyphenyl)-3-methoxypropenoate. Drycaesium fluoride (0.13 g, 0.84 mmol) and a catalytic amount of18-crown-6 were added and the resulting mixture stirred overnight atroom temperature. The reaction mixture was filtered and evaporated togive a thick oil (0.45 g). Chromatography (eluent diethylether-n-hexane, 2:1) afforded the title compound as a white, waxy solid(0.39 g). Trituration with n-hexane gave a white powder (0.26 g, 59%);m.p. 67°-70° C.; ¹ H NMR (CDCl₃) δ 3.55(3H,s); 3.63(3H,s); 3.68(3H,s);3.77(3H,s); 7.10-7.41(8H,m); 7.42(1H,s); 7.52(1H,s) ppm; mass spectrumm/e 527 (M⁺).

EXAMPLE 9

This Example illustrates the preparation of: ##STR25##

To the product of Example 8 (0.15 g, 0.284 mmol) in dry THF (3 ml) at 0°C. under nitrogen, were added potassium carbonate (0.039 g, 0.284 mmol)and some 4 Å molecular sieves. A solution containing freshly distilledphenol (0.027 mg, 0.284 mmol) in dry THF (1 ml) was added dropwise withstirring and the reaction mixture stirred overnight at room temperature.More phenol (0.027 mg, 0.284 mmol) and potassium carbonate (0.039 g,0.284 mmol) were added and stirring continued over the weekend. Thereaction mixture was poured into water (8 ml) and then extracted withdichloromethane (3×15 ml). The combined extracts were dried andevaporated to give a brown oil (0.18 g). Chromatography (eluent diethylether-n-hexane, 3:2) gave an oil (67 mg) which was re-chromatographed(eluent ethyl acetate-n-hexane-acetic acid, 2:7:0.1) to afford (afterwashing with base to remove traces of acetic acid) the title compound asa waxy gum (37 mg); ¹ H NMR (CDCl₃) δ 3.55(3H,s); 3.70(3H,s);7.10-7.48(9H,m); 7.41(1H,s) ppm; Infrared max. 1708, 1631 cm⁻¹ ; massspectrum m/e 413 (M³). A repeat preparation on a larger scale (1.71mmol) yielded the product as a yellow foam (0.44 g).

EXAMPLE 10

This Example illustrates the preparation of (E)-methyl2-[2-(5-phenoxy-1,2,4-triazin-3-yloxy)phenyl]-3-methoxypropenoate(Compound No. 115 of Table I).

To the product of Example 9 (0.30 g, 0.725 mmol) in THF (20 ml) wereadded potassium carbonate (0.35 g, 2.54 mmol), 5% palladium on carbon(45 mg) and then water (1.5 ml). Hydrogen gas was then bubbled throughthe stirred mixture at room temperature. After 31/2 hours, the mixturewas diluted with water (15 ml) and dichloromethane (20 ml) and filtered.The dichloromethane layer was separated and the aqueous layer wasextracted further with dichloromethane (2×20 ml). The combined organicextracts were dried, filtered and evaporated to give a pale yellow oil(0.44 g). Chromatography (eluent diethyl ether-n-hexane, 3:1) gave awaxy white foam (0.18 g) which crystallised from cold diethylether-n-hexane (containing a trace of dichloromethane) to afford thetitle compound as a white powder (0.17 g, 63%); m.p. 78°-80° C.;Infrared max. 1708, 1631 cm⁻¹ ; ¹ H NMR (CDCl₃) δ 3.56(3 H,s);3.70(3H,s); 7.13-7.47(9H,m); 7.41(1H,s); 8.79(1H,s) ppm; mass spectrumm/e 379 (M⁺).

The following are examples of compositions suitable for agricultural andhorticultural purposes which can be formulated from the compounds of theinvention. Such compositions form another aspect of the invention.Percentages are by weight.

EXAMPLE 11

An emulsifiable concentrate is made up by mixing and stirring theingredients until all are dissolved.

    ______________________________________                                        Compound No. 7 of Table I                                                                            10%                                                    Benzyl alcohol         30%                                                    Calcium dodecylbenzenesulphonate                                                                      5%                                                    Nonylphenolethoxylate (13 mole                                                                       10%                                                    ethylene oxide)                                                               Alkyl benzenes         45%                                                    ______________________________________                                    

EXAMPLE 12

The active ingredient is dissolved in methylene dichloride and theresultant liquid sprayed on to the granules of attapulgite clay. Thesolvent is then allowed to evaporate to produce a granular composition.

    ______________________________________                                        Compound No. 7 of Table I                                                                           5%                                                      Attapulgite granules 95%                                                      ______________________________________                                    

EXAMPLE 13

A composition suitable for use as a seed dressing is prepared bygrinding and mixing the three ingredients.

    ______________________________________                                        Compound No. 7 of Table I                                                                          50%                                                      Mineral oil           2%                                                      China clay           48%                                                      ______________________________________                                    

EXAMPLE 14

A dustable power is prepared by grinding and mixing the activeingredient with talc.

    ______________________________________                                        Compound No. 7 of Table I                                                                           5%                                                      Talc                 95%                                                      ______________________________________                                    

EXAMPLE 15

A suspension concentrate is prepared by ball milling the ingredients toform an aqueous suspension of the ground mixture with water.

    ______________________________________                                        Compound No. 7 of Table I                                                                          40%                                                      Sodium lignosulphonate                                                                             10%                                                      Bentonite clay        1%                                                      Water                49%                                                      ______________________________________                                    

This formulation can be used as a spray by diluting into water orapplied directly to seed.

EXAMPLE 16

A wettable powder formulation is made by mixing together and grindingthe ingredients until all are thoroughly mixed.

    ______________________________________                                        Compound No. 7 of Table I                                                                          25%                                                      Sodium lauryl sulphate                                                                              2%                                                      Sodium lignosulphonate                                                                              5%                                                      Silica               25%                                                      China clay           43%                                                      ______________________________________                                    

EXAMPLE 17

The compounds were tested against a variety of foliar fungal diseases ofplants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (no 1 or 2) in 4 cmdiameter minipots. The test compounds were formulated either by beadmilling with aqueous Dispersol T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, the formulations (100ppm active ingredient) were sprayed onto the foliage and applied to theroots of the plants in the soil. Alternatively, the compounds wereapplied as a foliar spray only at a concentration of 10 ppm or 25 ppm.The sprays were applied to maximum retention and the root drenches to afinal concentration equivalent to approximately 40 ppm a.i. in dry soil.Tween 20, to give a final concentration of 0.05%, was added when thesprays were applied to cereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the disease. An exception was the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment.Foliar pathogens were applied by spray as spore suspensions onto theleaves of test plants. After inoculation, the plants were put into anappropriate environment to allow infection to proceed and then incubateduntil the disease was ready for assessment. The period betweeninoculation and assessment varied from four to fourteen days accordingto the disease and environment.

The disease control was recorded by the following grading:

4=no disease

3=trace-5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants

The results are shown in Table VIII. In Table VIII the followingabbreviations are used:

Pr=Puccinia recondita (wheat)

Egh=Erysiphe graminis hordei (barley)

Egt=Erysiphe graminis tritici (wheat)

Sn=Septoria nodorum (wheat)

Vi=Venturia inaequalis (apple)

Po=Pyricularia oryzae (rice)

Tc=Thanatephorus cucumeris (rice)

Ca=Cercospora arachidicola (peanut)

Pv=Plasmopara viticola (vine)

Pil=Phytophthora infestans lycopersici (tomato)

                  TABLE VIII                                                      ______________________________________                                        COM-   TA-                                                                    POUND  BLE                                                                    No     No     Pr    Egh  Egt  Sn  Vi  Po  Tc  Ca  Pv  Pil                     ______________________________________                                         1     I      4a    4a   --   --  4a  3a  --  4a  4a  4a                       7     I      4     4    --   --  4   4   --  4   4   --                       11    I      4     4    --   --  4   4   --  4   4   4                        13    I      4     --   --   --  4   3   --  4   4   4                        15    I      4     2    --   --  4   4   --  2   4   4                       243    I      4     --   4    2   4   --  --  --  4   --                       1     II     0a    0a   --   0a  0b  0a  0b  --  3a  0b                      229    II     0     0    --   3   4   0   1   --  4   2                        1     III    --    4    --   --  4   3   --  4   4   4                       115    III    4a    3a   --   --  4a  2a  --  4a  4a  2a                      116    III    4     4    --   --  4   --  --  --  4   4                       119    III    4     --   4    4   4   4   --  --  4   --                      122    III    4a    --   0a   3a  4a  4a  --  --  4a  --                      123    III    3a    0a   --   --  3a  1a  --  3a  4a  0a                      143    III    4     4    --   --  4   4   --  --  4   4                       175    III    4     4    --   --  4   4   --  --  4   4                       178    III    4     4    --   3   4   4   4   --  4   3                       229    III    4     4    --   --  4   4   4   --  4   4                       230    III    4     --   4    4   4   4   4   --  4   4                       231    III    4     --   4    2   4   4   --  --  4   --                      1      IV     3     0    --   --  4   --  --  3   4   0                       2      IV     3     0    --   --  3   0   --  3   4   4                       3      IV     3     0    --   --  4   3   --  --  4   1                       4      IV     4     0    --   --  4   2   --  --  4   4                       5      IV     2     1    --   --  4   4   0   --  4   4                       6      IV     4     0    --   --  3   --  --  --  4   0                       7      IV     4     0    --   --  4   --  --  --  3   0                       8      IV     4     0    --   3   4   3   1   --  4   0                       9      IV     0     0    --   3   0   2   0   --  4   3                       10     IV     3     0    --   4   4   0   1   --  4   3                       2      V      0     0    --   3   0   0   0   --  4   1                       3      V      0a    --   0a   0a  1a  0a  0a  --  0a  0a                      ______________________________________                                         a 10 ppm foliar spray only                                                    6 25 ppm foliar spray only                                                    -- no result                                                             

We claim:
 1. A compound having the formula (I): ##STR26## in which L isnitrogen; one of K and M is nitrogen and the other is CY wherein Y is H,halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, cyano, nitro or trifluoromethyl; n is0 or 1; and X is optionally substituted phenyl or an optionallysubstituted heteroaromatic ring selected from the group consisting ofthiophene, pyrrole, imidazole, pyrazole, thiazole, isothiazole, oxazole,isoxazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,4-thiadiazole,1,3,4-thiadiazole, pyridine, pyrimidine, pyrazine, pyridazine,1,2,4-triazine and 1,3,5- triazine, the optional substituents of theoptionally substituted phenyl or heteroaromatic ring X being selectedfrom one or more of the group consisting of halogen, C₁₋₄ alkyl, C₃₋₆cycloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₂₋₄ alkenyloxy, C₂₋₄alkynyloxy, phenyl, benzyloxy, cyano, isocyano, thiocyanato,isothiocyanato, nitro, NR¹ R², NR¹ OR², N₃, NHCOR¹, NR¹ COR², NHCONR¹R², N═CHNR¹ R², NHSO₂ R¹, OR¹, OCOR¹, OSO₂ R², SR¹ , SOR¹, SO₂ R¹, SO₂OR¹, SO₂ NR¹ R², COR¹, CR¹ ═NOR², CHR¹ CO₂ R², CO₂ R¹, CONR1R², CSNR¹R², CH₃ O₂ C.C:CH.OCH₃, 1-(imidazol-1-yl)vinyl, furyl, thienyl,pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl,isoxazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, 1,2,4-thiadiazolyl,1,3,4-thiadiazolyl, pyrindinyl, pyrimidinyl, pyrazinyl, pyridazinyl,1,2,4-triazinyl or 1,3,5-triazinyl or, when X is phenyl, twosubstituents ortho to one another, joint to form a fused benzene,pyridine, thiophene or imidazole ring or a methylenedioxy group; R¹ andR² being independently hydrogen C₁₋₄ alkyl, C₁₋₄ alkenyl or phenyl; andany of the foregoing aliphatic moieties being optionally substitutedwithone or more of halogen, cyano, OR¹, SR¹, NR¹ R², SiR¹ ₃, or OCOR¹and any of the foregoing phenyl moieties being optionally substitutedwith one or more of halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, nitro or cyano. 2.A compound according to claim 1 in wich Y is H or halogen.
 3. A compoundaccording to claim 1 in which Y is H or chloro.
 4. A compound accordingto claim 1 in which Y is H.
 5. A compound according to claim 1 in whichM is nitrogen and Y is H.
 6. The (E)-isomer of a compound according toclaim
 1. 7. A compound according to claim 1 in which the optionalsubstituents of the optionally substituted phenyl or heteroaromatic ringX are selected from one or more of the group consisting of halogen, C₁₋₄alkyl, C₃₋₆ cycloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₂₋₄ alkenyloxy,C₂₋₄ alkynyloxy, phenyl, benzyloxy, cyano, isocyano, thiocyanato,isothiocyanato, nitro, NR¹ R², NHCOR¹, NHCONR¹ R², NHSO₂ R¹, OR¹, OCOR¹,OSO₂ R¹, SR¹, SOR¹, SO₂ R¹, COR¹, CR¹ ═NOR², CO₂ R¹, CONR¹ R², CSNR¹ R²; or, when X is phenyl, two substituents ortho to one another, join toform a fused benzene, pyridine, thiophene, or imidazole ring or amethylenedioxy group; R¹ and R² being independently hydrogen, C₁₋₄ alkylor phenyl; aliphatic moieties of any of the substituents beingthemselves optionally substituted with one or more of halogen, cyano,OR¹ or OCOR¹ and the phenyl moieties of any of the substituents beingthemselves optionally substituted with one or more of halogen, C₁₋₄alkyl, C₁₋₄ alkoxy, nitro or cyano.
 8. A compound according to claim 7in which M is nitrogen and Y is H.
 9. A compound according to claim 7 inwhich M is nitrogen, Y is H and n is
 0. 10. A compound formula (I.1):##STR27## in which Y is H or chlorine and Q is H, halogen, cyano, nitroor trifluoromethyl.
 11. A compound according to claim 10 in which Y isH.
 12. A compound of formula (I.2): ##STR28## in which Q is H, halogen,cyano, nitro or trifluoromethyl.
 13. A fungicidal composition comprisinga fungicidally effective amount of a compound according to claim 1 and afungicidally acceptable carrier or diluent therefor.
 14. A method ofcombating fungi which comprises applying to plants, to the seeds ofplants or to the locus of the plants or seeds, a fungically effectiveamount of a compound according to claim 1.